JP2002030210A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition capable of obtaining a molding having an excellent low-temperature impact strength, moldability and flame reststance. SOLUTION: This thermoplastic resin composition includes (A) a polycarbonate resin, (B) a composite rubber based graft copolymer obtained by graft polymerizing one or more kind of vinyl monomers to a composite rubber comprising a polyorganosiloxane component and a polyalkyl(meth)acrylate and (C) a rubber like polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent impact resistance and moldability.

[0002]

2. Description of the Related Art Polycarbonate resins are thermoplastic resins having excellent heat resistance and impact resistance, and are used in various kinds of thermoplastic resin alloys in combination with other thermoplastic resins. However, it is known that these thermoplastic resin alloys are inferior in impact resistance, and various methods have been conventionally proposed. For example, Japanese Patent Publication No. 55-9435 discloses polycarbonate resin, polyester resin,
And a resin composition comprising a butadiene-based graft polymer have been proposed. Although such resin compositions have been somewhat successful in improving impact resistance, they have the disadvantage of essentially inferior weatherability. JP-A-53-129246 proposes a resin composition comprising a polycarbonate resin, a polyester-based resin, and an acrylate-based copolymer, but has a drawback of low impact strength at low temperatures. . Further, JP-A-1-230664 discloses a composite rubber system obtained by graft-polymerizing a vinyl monomer onto a polycarbonate resin, a polyester resin, and a composite rubber comprising a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component. A resin composition comprising a graft copolymer has been proposed. Low temperature impact strength and weather resistance are improved.

Japanese Patent Application Laid-Open No. 4-325553 discloses that a composite rubber-based graft copolymer and a specific phosphate ester are used for PC and a polyester-based resin (sometimes referred to as PEs) to provide excellent heat stability. PC / PEs alloys. However, there is no detailed description of flame retardancy.

Japanese Patent Application Laid-Open No. 8-269314 discloses that a system in which a composite rubber-based graft copolymer is added to an alloy of PC and a (meth) acrylic resin has improved weather resistance, impact resistance, heat resistance, and moldability. It discloses that it is excellent. However, there is no detailed description of flame retardancy.

Japanese Patent Application Laid-Open No. Hei 6-322545 discloses a PC
(20 to 80% by mass) and a copolymer (80 to 20% by mass) of a copolymer obtained by grafting two or more kinds of vinyl monomers to a diene rubber (80 to 20% by mass) and a composite rubber-based graft copolymer or composite It discloses that a system in which a mixture of a rubber-based graft copolymer and a vinyl-based polymer is added in an amount of 1 to 50 parts by mass has excellent plating properties. However, there is no detailed description about flame retardancy.

Japanese Unexamined Patent Publication (Kokai) No. 9-12855 discloses that when a small amount of a composite rubber (based graft copolymer) (0.5 to 8% by mass) is added to PC, one of the impact tests of the impact test becomes good. Is disclosed. However, there is no detailed description of flame retardancy.

JP-A-9-12856 discloses a resin obtained by adding a composite rubber-based graft copolymer (0.1 to 15% by mass) to an alloy of PC and a small amount of polyolefin (0.1 to 5% by mass). It discloses that the composition has good surface impact after painting. However, there is no detailed description of flame retardancy.

[0008] Japanese Patent No. 2860856, JP-A-8-3
No. 397 examines the performance when a composite rubber-based graft copolymer is added to PC and ABS resin alloy and further when a flame retardant is added, and discloses that it is excellent in impact resistance and further flame retardancy. ing.

Japanese Patent Application Laid-Open No. 7-173401 discloses a method for improving the dripping resistance of a composite rubber-based graft copolymer in a system in which a flame retardant is added to a thermoplastic resin.
0.35 parts by mass of a resin composition,
It discloses that it has excellent impact resistance performance.

Japanese Patent Application Laid-Open No. 7-179673 discloses that a rubber and a vinyl polymer-containing reinforced resin (for example, AB
S, AAS, HIPS), 0.1 to 30 parts by mass of a phosphorus-based flame retardant, 0.01 to 30 parts by mass of a composite rubber-based graft copolymer as an anti-dripping agent in 100 parts by mass of an alloy containing
A halogen-free resin having flame retardancy and impact resistance when added at 0.35 parts by mass is disclosed.

JP-A-8-34916 discloses a flame-retardant resin composition obtained by adding a phosphorus compound, a phenolic polymer and a silicon-containing compound to a PC-containing thermoplastic resin. The composite rubber-based graft copolymer is disclosed as having both a thermoplastic resin and a silicon-containing compound.Here, the idea of using the composite rubber-based graft copolymer with a silicon-containing compound other than the composite rubber-based graft copolymer is not considered. Absent. Japanese Patent Application Laid-Open No. 8-34926 discloses the same contents for a thermoplastic resin. However, the composite rubber-based graft copolymer is disclosed as having both a thermoplastic resin and a silicon-containing compound. There is no idea to use the polymer together with a silicon-containing compound other than the composite rubber-based graft copolymer.

Japanese Patent Application Laid-Open No. Hei 8-295796 discloses that a phosphorus-containing compound is added to a PC-containing thermoplastic resin having a specific molecular weight and viscosity, and that at least one selected from a silicon-containing compound, a phenolic polymer and a fluorine-containing resin is used. It discloses a flame retardant resin composition to which one kind is added. Here also, the composite rubber-based graft copolymer is disclosed as a combination of a thermoplastic resin and a silicon-containing compound, and the composite rubber-based graft copolymer is used together with a silicon-containing compound other than the composite rubber-based graft copolymer. I have no idea.

Japanese Patent Application Laid-Open No. 8-319387 discloses that PC and an AS resin having a specific molecular weight and / or a relative viscosity, a graft rubber polymer and a phosphorus compound are added, and further, a silicone, a phenol polymer and a fluorine resin are added. It discloses a flame-retardant resin composition to which at least one selected is added. A composite rubber-based graft copolymer is disclosed as an example as one of the graft rubbery polymers.

JP-A-8-319388 discloses that PC and a styrene-based resin, a specific AS-grafted rubbery polymer and a phosphorus-based compound are added, and further selected from silicones, phenol-based polymers, and fluorine-based resins. It discloses a flame-retardant resin composition to which at least one is added. In the specification, the composite rubber-based graft copolymer is only slightly described as one of the graft rubbery polymers.

JP-A-8-325449 discloses thermoplastic resins containing PC (PC / ABS, PC / PBT / AB).
Disclosed is a flame-retardant resin composition in which a specific phosphorus compound is added to S), and at least one selected from silicone, phenolic polymer, and fluororesin is added. The specific phosphorus-based compound used here is a phosphorus-based compound used for a PC-based resin. In the specification, the composite rubber-based graft copolymer is slightly described as a resin other than PC.

Japanese Patent Application Laid-Open No. 8-59502 discloses a method in which a phosphorus-based compound and a metal deactivator are added to a PC-containing thermoplastic resin and at least one selected from a silicon-containing compound, a phenolic polymer, and a fluorine-based resin is used. Disclosed is an added flame retardant resin composition. Here also, the composite rubber-based graft copolymer is disclosed as a combination of a thermoplastic resin and a silicon-containing compound, and the composite rubber-based graft copolymer is used together with a silicon-containing compound other than the composite rubber-based graft copolymer. I have no idea.

However, nothing is specified about the impact resistance and moldability of the PC-containing resin composition other than the above-mentioned publication or a system in which the above-mentioned resin composition is further complicated, and there is no suggestion. I can't.

[0018]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition capable of obtaining a molded article having excellent low-temperature impact strength, moldability and flame retardancy.

[0019]

That is, the gist of the present invention is to provide a composite rubber comprising a polycarbonate resin (A), a polyorganosiloxane component and a polyalkyl (meth) acrylate component with one or more vinyl monomers. A thermoplastic resin composition comprising a composite rubber-based graft copolymer (B) obtained by graft polymerization of a monomer and a rubbery polymer.

Further, the thermoplastic resin composition is selected from olefin resins (D-1), polyester resins (D-2), polyphenylene ether resins (D-3) and vinyl resins (D-4). And a thermoplastic resin composition in which at least one kind is blended, and a thermoplastic resin composition in which a flame retardant (E) is blended with the thermoplastic resin composition.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The polycarbonate resin (A) used in the present invention is a polycarbonate produced using dihydroxydiphenylalkane as a main raw material. Bisphenols and a carbonate precursor such as phosgene or diaryl carbonate are prepared by a phosgene method or a transesterification method. And obtained by reacting Examples of bisphenols include 2,2- (4,4'-dihydroxydiphenyl) propane (= bisphenol A), and a part or all of the
4'-dihydroxydiphenylalkane, or 4,
It may be replaced with 4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylether or the like, or two or more kinds may be used in combination.

The composite rubber-based graft copolymer (B) used in the present invention comprises a composite rubber comprising a polyorganosiloxane component and a polyalkyl (meth) acrylate component, and one or more types of rubber containing a vinyl monomer. It is a product obtained by graft polymerization of a vinyl monomer.

The two types of components constituting the composite rubber include a polyorganosiloxane rubber component of 1 to 99% by mass and a polyalkyl (meth) acrylate component of 99 to 1% by mass (however, the total amount of both components is 100% by mass). %).

The above composite rubber may be produced by any method, but the emulsion polymerization method is most suitable. First, a latex of polyorganosiloxane is prepared, and then a monomer for synthesizing alkyl (meth) acrylate is prepared. Is preferably impregnated into particles of a polyorganosiloxane latex, and then the synthesis monomer is polymerized.

The polyorganosiloxane rubber component constituting the composite rubber can be prepared by emulsion polymerization using an organosiloxane and a crosslinking agent (CI) shown below. At this time, a graft crosslinking agent (GI) is further added. They can be used together.

Examples of the organosiloxane include various cyclic members having three or more membered rings.
A 6-membered ring. For example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like, These may be used alone or in combination of two or more. These are used in an amount of 5% in the polyorganosiloxane component.
0 mass% or more, preferably 70 mass% or more.

As the crosslinking agent (CI), trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, Tetrabutoxysilane or the like is used. Particularly, a tetrafunctional crosslinking agent is preferable, and among them, tetraethoxysilane is particularly preferable. The amount of the crosslinking agent used is 0.1 to 30% by mass in the polyorganosiloxane component.

As the graft-linking agent (GI), a compound capable of forming a unit represented by the following formula is used.

CH ₂ ＣC (R 2) —COO— (CH ₂ ) _p —SiR _{1 n} O _{(3-n) / 2} (GI-1) CH ₂ ＣC (R 2) —C ₆ H ₄ —SiR _{1 n} O _{(3-n) / 2 (} GI -2) CH 2 = CH- SiR1 n O (3-n) / 2 (GI -3) HS- (CH 2) p- SiR1 n O (3-n) / 2 (GI-4) (wherein, R 1 represents a methyl group, an ethyl group, a propyl group, or a phenyl group, R 2 represents a hydrogen atom or a methyl group, n represents 0, 1 or 2, and p represents a number of 1 to 6. .) The (meth) acryloyloxysiloxane capable of forming the unit of the above formula (GI-1) has a high grafting efficiency and can form an effective graft chain, and is advantageous in terms of the development of impact resistance. is there.

It is to be noted that methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of the above formula (GI-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl Examples thereof include ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and γ-methacryloyloxybutyldiethoxymethylsilane.

Vinyl siloxane is mentioned as one capable of forming the unit of the above formula (GI-2), and specific example is tetramethyltetravinylcyclotetrasiloxane.

One which can form the unit of the above formula (GI-3) is p-vinylphenyldimethoxymethylsilane. Examples of the unit capable of forming the unit of the formula (GI-4) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, and γ-mercaptopropyldiethoxymethylsilane.

The amount of the grafting agent to be used is 0 to 10% by mass, preferably 0.5 to 5% by mass in the polyorganosiloxane component.

For the production of the latex of the polyorganosiloxane component, a method described in, for example, US Pat. Nos. 2,891,920 and 3,294,725 can be used. In the practice of the present invention, for example, a mixed solution of an organosiloxane and a crosslinking agent (CI) and, if desired, a graft crosslinking agent (GI) are mixed with a homogenizer in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid. It is preferable to produce by a method of shear-mixing with water using the method described above.
Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier for the organosiloxane and also serves as a polymerization initiator. At this time, it is preferable to use a metal salt of an alkyl benzene sulfonic acid, a metal salt of an alkyl sulfonic acid or the like in combination, since this is effective for stably maintaining the polymer during graft polymerization.

Next, the polyalkyl (meth) acrylate component constituting the composite rubber can be synthesized using the following alkyl (meth) acrylate, a cross-linking agent (CII), and a graft crossing agent (GII). .

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, 2-
Examples thereof include alkyl acrylates such as ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. The use of n-butyl acrylate is particularly preferable.

Examples of the crosslinking agent (CII) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.

Examples of the graft crosslinking agent (GII) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent. These crosslinking agents and graft crossing agents are used alone or in combination of two or more. The total amount of the crosslinking agent and the graft crosslinking agent used is 0.1 to 20% by mass in the polyalkyl (meth) acrylate component.

The polymerization of the polyalkyl (meth) acrylate component is carried out by adding the above alkyl (meth) acrylate into a latex of a polyorganosiloxane component that has been neutralized by adding an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate. After adding a crosslinking agent and a graft-linking agent to impregnate the polyorganosiloxane particles, the reaction is carried out by the action of a usual radical polymerization initiator. As the polymerization proceeds, a composite rubber latex of the polyorganosiloxane component and the polyalkyl (meth) acrylate component is obtained. In the practice of the present invention, as the composite rubber, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the main skeleton of the polyalkyl (meth) acrylate component has a repeating unit of n-butyl acrylate. Composite rubber is preferably used.

Examples of the vinyl monomer of the composite rubber-based graft copolymer (B) used in the present invention include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; methyl methacrylate, 2-ethylhexyl methacrylate; Methacrylates such as glycidyl methacrylate; acrylates such as methyl acrylate, ethyl acrylate, n-butyl acrylate and glycidyl methacrylate; and various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These are used in combination of one or more. Among these vinyl monomers, methyl methacrylate, butyl acrylate, acrylonitrile, and styrene are preferably used.

Further, the composite rubber-based graft copolymer (B)
Is preferably 2 to 50% by mass, more preferably 5 to 30% by mass of the composite rubber-based graft copolymer (B). . When the amount of the component is less than 2% by mass, the development of impact resistance becomes insufficient. On the other hand, if the content exceeds 50% by mass, the content of rubber is reduced, so that in this case also, the expression of impact resistance becomes insufficient.

The composite rubber-based graft copolymer (B) used in the present invention is obtained by adding the above-mentioned vinyl monomer to a composite rubber latex and polymerizing it in one or more stages by a radical polymerization technique. The copolymer (B) latex can be separated and recovered by throwing it into hot water in which metal salts such as calcium chloride, magnesium sulfate, and aluminum sulfate are dissolved, salting out and coagulating.

In the graft polymerization, a free polymer, which is obtained by polymerizing a component corresponding to a branch of the graft copolymer only with the branch component without grafting to the trunk component, is partially produced as a by-product,
It is obtained as a mixture of a graft copolymer and a free polymer. In the present invention, these are collectively referred to as a graft copolymer.

Examples of the rubbery polymer (C) used in the present invention include diene such as methyl methacrylate / butadiene / styrene copolymer resin (MBS resin) and acrylonitrile / butadiene / styrene copolymer resin (ABS resin). Core-shell type rubbery polymer, acrylate / styrene / acrylonitrile copolymer resin (ASA resin), acrylic core-shell type rubbery polymer such as acrylate / methyl methacrylate copolymer resin, silicone / acrylate / methyl methacrylate copolymer Resin, silicone-based core-shell type rubbery polymer such as silicone / acrylate / acrylonitrile / styrene copolymer resin,
Ethylene / propylene copolymer (EPR), ethylene /
Olefins such as butene-1 copolymer, ethylene / propylene / non-conjugated diene copolymer (EPDM), ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl (meth) acrylate copolymer (EEA) Thermoplastic elastomer (TPO), styrene / butadiene / styrene block copolymer (SBS), styrene / ethylene / butylene / styrene block copolymer (SEBS), styrene / ethylene / propylene block copolymer (SE
P), styrene / isoprene / styrene copolymer (SI
S) and other styrene-based thermoplastic elastomers (TPE);
And their modified products such as maleic anhydride and glycidyl methacrylate, and thermoplastic polyesters (TPE
s), thermoplastic polyurethane (TPU), isobutene /
Isoprene rubber (IIR), polyisoprene (IR),
Natural rubber (NR), butadiene / acrylonitrile copolymer (NBR), butadiene / styrene copolymer (SB
R), and the like. These can be used in combination of two or more.

The olefin resin (D-
1) as polypropylene, low density polyethylene,
Examples include high-density polyethylene, polymethylpentene-1, ethylene-propylene copolymer, and the like.

The polyester resin (D-2) used in the present invention is a resin obtained by a condensation reaction using an aromatic dicarboxylic acid or an ester-forming derivative thereof and an alkylene glycol as main components, for example, terephthalic acid. , Isophthalic acid, a dicarboxylic acid such as naphthalenedicarboxylic acid, and ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, obtained by reacting with a glycol such as cyclohexane dimethanol, obtained as needed, other dicarboxylic acids and A small amount of glycol may be copolymerized. Such polyester resins include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and copolymers or mixtures thereof.

As a specific example of the polyphenylene ether resin used in the present invention, poly (2,6-dimethyl-
1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-
Methyl-6-ethyl-1,4-phenylene) ether,
Poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,
4-phenylene) ether, (2,6-dimethyl-1,
A copolymer of (4-phenylene) ether and (2,3,6-trimethyl-1,4-phenylene) ether;
6-diethyl-1,4-phenylene) ether and (2,
Copolymer with 3,6-trimethyl-1,4-phenylene) ether, (2,6-dimethyl-1,4-phenylene) ether and (2,3,6-triethyl-1,4-phenylene) ether And the like.

The vinyl resin used in the present invention (D-
4) is (meth) acrylate-based resin, (meth) acrylate-aromatic vinyl-based resin, (meth) acrylate-
Vinyl cyanide resin, (meth) acrylate-vinyl cyanide-aromatic vinyl resin, (meth) acrylate-olefin resin, aromatic vinyl resin, aromatic vinyl resin-olefin resin.

In the thermoplastic resin composition of the present invention,
(A) component, (B) component, and (C) component are 50 ~ each.
It is preferable to contain 85% by mass, 1 to 20% by mass, and 1 to 30% by mass. Further, the components (A), (B), and (C) are each 60 to 80% by mass,
%, Preferably 2 to 20% by mass.
When the amount of the component (B) is less than 1% by mass, the development of impact strength becomes insufficient. On the other hand, when the amount exceeds 20% by mass, the strength, rigidity and heat resistance of a molded article from the composition may be impaired.

Further, (D-1), (D-2), (D-
At least one component selected from 3) and (D-4) is used in the thermoplastic resin composition of the present invention in an amount of 5 to 50.
It is preferable that the content is contained by mass%. Furthermore, 7-20
It is preferable that the content is contained by mass%.

In the thermoplastic resin composition of the present invention, a flame retardant (E) can be used if necessary.

As the flame retardant (E), tetrabromobisphenol A (TBA), TBA polycarbonate oligomer, TBA tribromophenol, TBA epoxy oligomer, brominated polystyrene, chlorinated paraffin,
Halogen flame retardants such as dechlorane plus, phosphoric esters such as triphenyl phosphate, tricresyl phosphate, halogen-containing phosphoric ester, condensed phosphoric ester, phosphoric amide, red phosphorus, ammonium polyphosphate, phosphazene Phosphorus flame retardants such as compounds, nitrogen flame retardants such as triazine compounds, metal salts such as zinc borate, hydrated metal compounds such as aluminum hydroxide and magnesium hydroxide, and metal oxides such as antimony trioxide Inorganic flame retardants, and silicone-based flame retardants.

When the flame retardant (E) is blended, (A) +
(B) + (C) ((A) + (B) + (C) + (D−
1), (D-2), (D-3) and (D-4) at least one) = 100 parts by mass,
It is preferable to add 300 parts by mass.

In the thermoplastic resin composition of the present invention,
If necessary, a filler can be blended in order to further improve the heat resistance and mechanical strength of the composition. As the filler, fibrous, particulate, powdery and other shapes can be used, and as such a filler, glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, aramid fiber , Barium sulfate, calcium sulfate, calcium silicate, calcium carbonate, magnesium carbonate, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, mica, talc, kaolin, pyrophyllite, bentonite, sericite , Zeolite, wollastonite, ferrite, graphite, gypsum, glass beads, glass balloons, quartz and the like.

When a filler is blended, (A) + (B)
+ (C) ((A) + (B) + (C) + (D-1), (D
It is preferable to add 1 to 300 parts by mass based on 100 parts by mass of (-2), (D-3) and (D-4)).

The thermoplastic resin composition according to the present invention may contain, according to the purpose, compounding, kneading and molding of the resin, conventional stabilizers, lubricants, plasticizers and pigments, as long as the physical properties are not impaired. , Heat resistance improver, release agent,
Crystal nucleating agent, fluidity improver, antistatic agent, conductivity imparting agent,
Surfactants, compatibilizers, anti-fogging agents, foaming agents, antibacterial agents and the like can be added.

The method of mixing the thermoplastic resin composition in the present invention is not particularly limited, and powders and granules are mixed by a known technique, for example, a Henschel mixer or a tumbler, and the mixture is extruded by an extruder or kneader. And various methods such as a method of melting and mixing with a mixer or the like, a method of sequentially mixing other components with a component previously melted, and a method of directly molding a mixture with an injection molding machine.

The resin molded article of the present invention can be obtained from the thermoplastic resin by a usual molding method such as an injection molding method and an extrusion molding method.

Further, it can be cast into a film by dissolving it in a solvent or the like and used as a coating film.

[0061]

The present invention will be described in more detail with reference to the following examples and comparative examples. "%" And "part" in the description
Represents "% by mass" and "parts by mass", respectively.

The evaluation of physical properties and performance in each of the examples and comparative examples was carried out under the absolute drying conditions by the following methods.

(1) Average particle diameter; quasi-elastic light scattering method (MA
According to VERN SYSTM 4600, measurement temperature 25 ° C., scattering angle 90 °), a sample solution was prepared by diluting the latex with water.

(2) Izod impact strength; ASTM D
It was measured according to the method of 256. (1/4 ", notched; unit: J / m) (3) Fluidity: Measured spiral flow length of 2 mmt under conditions of 250 ° C. and 98 MPa.

(4) Flame retardancy: Measured according to the method of UL94. (3.2 mmt) (Reference Example 1) Production of Composite Rubber Graft Copolymer (B-1) 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane, and 97 parts of octamethylcyclotetrasiloxane 5 parts were mixed to obtain 100 parts of a siloxane mixture. 100 parts of the above mixed siloxane was added to 200 parts of distilled water in which 0.67 part of sodium dodecylbenzenesulfonate and 0.67 part of dodecylbenzenesulfonic acid were respectively dissolved.
After preliminary stirring at 000 rpm, the mixture was emulsified and dispersed with a homogenizer at a pressure of 200 kg / cm 2 to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, then left at 20 ° C., and after 48 hours, the pH of this latex was adjusted to 7.0 using an aqueous sodium hydroxide solution. 0, complete the polymerization and obtain a polyorganosiloxane latex (hereinafter referred to as PDM
Called S-1. ) Got. The polymerization rate of the obtained polyorganosiloxane was 89.1%, and the average particle size of the polyorganosiloxane was 0.19 μm. This PDMS-1 was coagulated and dried with isopropanol to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was determined to be 91.4%.

35 parts of this PDMS-1 was collected and placed in a separable flask equipped with a stirrer, 175 parts of distilled water was added, the atmosphere was replaced with nitrogen, the temperature was raised to 50 ° C., and n-butyl acrylate 78.4 was added. Part, allyl methacrylate 1.6
And a mixture of 0.3 parts of tert-butyl hydroperoxide were charged and stirred for 30 minutes, and the mixture was permeated into the polyorganosiloxane particles. Then, sulfuric acid 1
0.002 part of iron, 0.006 part of disodium ethylenediaminetetraacetic acid, 0.3 part of Rongalit and 1 part of distilled water
0 parts of the mixed solution was charged to start radical polymerization, and then kept at an internal temperature of 70 ° C. for 2 hours to complete the polymerization to obtain a composite rubber latex. A part of this latex was collected and the average particle diameter of the composite rubber was measured to be 0.22 μm.
Further, this latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 4 hours, and the gel content was measured.
%Met.

A mixture of 10 parts of methyl methacrylate and 0.024 part of tert-butyl hydroperoxide was added dropwise to this composite rubber latex at 60 ° C. for 15 minutes, and then kept at 60 ° C. for 2 hours to form a composite rubber latex. The graft polymerization of was completed. The polymerization rate of methyl methacrylate was 98.5%. The average particle size of the graft copolymer latex was 0.24 μm. The obtained graft copolymer latex was added at 40 ° C. so that the ratio of a 5% -concentration aqueous calcium chloride solution was 1: 2.
The temperature was raised to 90 ° C. to coagulate, and after repeating washing with water, the solid content was separated and dried at 80 ° C. for 24 hours to obtain a dry powder of the composite rubber-based graft copolymer (B-1).

Reference Example 2 Preparation of Composite Rubber Graft Copolymer (B-2) 280 parts of PDMS-1 was collected, placed in a separable flask equipped with a stirrer, and purged with nitrogen. The temperature was raised to 8.4 parts of n-butyl acrylate, 1.6 parts of allyl methacrylate and 0.3 part of cumene hydroperoxide.
Of the mixed solution was stirred for 30 minutes, and the mixed solution was permeated into the polyorganosiloxane particles. Next, a mixed solution of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.3 part of Rongalit and 10 parts of distilled water was charged to start radical polymerization. After holding for a while, the polymerization was completed to obtain a composite rubber latex. A part of this latex was collected and the average particle diameter of the composite rubber was measured to be 0.19 μm. The latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 4 hours, and the gel content was measured to be 95%.

A mixture of 10 parts of methyl methacrylate and 0.024 part of tert-butyl hydroperoxide was added dropwise to the composite rubber latex at 60 ° C. for 15 minutes, and then kept at 60 ° C. for 2 hours to form a composite rubber latex. The graft polymerization of was completed. The polymerization rate of methyl methacrylate was 98.5%. The average particle size of the graft copolymer latex was 0.20 μm. The obtained graft copolymer latex was added at 40 ° C. so that the ratio of a 5% -concentration aqueous calcium chloride solution was 1: 2.
The temperature was raised to 90 ° C. to solidify, and after repeated washing with water, the solid content was separated and dried at 80 ° C. for 24 hours to obtain a dry powder of the composite rubber-based graft copolymer (B-2).

Reference Example 3 Production of Composite Rubber Graft Copolymer (B-3) 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 99.5 parts of octamethylcyclotetrasiloxane were mixed to give a siloxane. 100 parts of the mixture were obtained. To this was added 200 parts of distilled water in which 0.67 part of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred with a homomixer at 10,000 rpm for 2 minutes, and then passed twice through a homogenizer at a pressure of 30 MPa to obtain a stable premix. An organosiloxane latex was obtained. On the other hand, 10 parts of dodecylbenzenesulfonic acid and 190 parts of distilled water were charged into a separable flask equipped with a cooling condenser, and 5%
Of dodecylbenzenesulfonic acid was prepared.

While this aqueous solution was heated to 85 ° C., 300 parts of a premixed organosiloxane latex was added dropwise over 2 hours, and after the addition was completed, the temperature was maintained for 2 hours and then cooled. The reaction was then kept at room temperature for 12 hours and neutralized with caustic soda to adjust the pH to about 7.

The latex PDM thus obtained
S-2 was dried at 170 ° C. for 30 minutes to obtain a solid content, which was 18.8%. Number average particle size is 0.04μ
m, the standard deviation of the particle size distribution was 0.01.

106 parts of this PDMS-2 was collected and placed in a separable flask equipped with a stirrer, 204 parts of distilled water was added, the atmosphere was replaced with nitrogen, and the temperature was raised to 50 ° C. to give 54.9 n-butyl acrylate. Parts, allyl methacrylate 0.
1 part and tert-butyl hydroperoxide 0.2
Two parts of the mixed liquid was charged and stirred for 30 minutes, and the mixed liquid was permeated into the polyorganosiloxane particles. Next, a mixed solution of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.3 part of Rongalit and 10 parts of distilled water was charged to start radical polymerization. After holding for a while, the polymerization was completed to obtain a composite rubber latex. A part of this latex was collected and the average particle diameter of the composite rubber was measured to be 0.06 μm. Further, this latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 4 hours, and the gel content was measured to be 90%.

To this composite rubber latex, a mixture of 25 parts of methyl methacrylate and 0.125 part of tert-butyl hydroperoxide was added dropwise at 60 ° C. for 25 minutes, and then kept at 60 ° C. for 2 hours. The graft polymerization of was completed. The polymerization rate of methyl methacrylate was 98.5%. The average particle size of the graft copolymer latex was 0.07 μm. The obtained graft copolymer latex was added at 40 ° C. so that the ratio of a 5% -concentration aqueous calcium chloride solution was 1: 2.
The temperature was raised to 90 ° C. to coagulate, and after washing with water was repeated, the solid content was separated and dried at 80 ° C. for 24 hours to obtain a dry powder of the composite rubber-based graft copolymer (B-3).

Novarex 7025A (manufactured by Mitsubishi Engineering-Plastics Co., Ltd.) was used as a polycarbonate resin, and a thermoplastic resin, a graft copolymer (B-1 to B-3), a phosphate ester-based flame retardant ( A twin screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM-
35B), melt-kneading at a cylinder temperature of 260 ° C., pelletizing, drying the resulting pellet, and then using an injection molding machine (Promat injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.)
The test piece was molded at a cylinder temperature of 280 ° C. to evaluate impact resistance and fluidity. The results are shown in Tables 1 to 4.

The components other than the components (A) and (B) are shown below.

(C): MBS: Mitsubishi Rayon Co., Ltd. Metablen C223A ABS: Acrylonitrile / styrene grafted butadiene rubber (70% rubber content) TPE: Toyobo Co., Ltd. Perprene S2000 SEBS: Shell Chemical Co., Ltd. Clayton G1650 EMMA: Ethylene methyl methacrylate resin Sumitomo Chemical Co., Ltd. Acrif WK402 (D-1): PP: Polypropylene resin Nippon Polychem Co., Ltd. Novatec PP MA2 (D-2): PBT: Mitsubishi Rayon Co., Ltd. Toughpet N1000 PET: Polyethylene terephthalate Mitsubishi Rayon Co., Ltd. KR582 (D-3): PPE: (2,6-dimethyl-1,4-phenylene) ether (reduced viscosity (ηsp / c) = 0.56 dl / g) (D-4): MS: Methyl methacrylate Ren resin Nippon Steel Chemical Co., Ltd. Estyrene MSMS600 SAN: Acrylonitrile / styrene resin Asahi Kasei Corporation AP789 PS: Sumitomo Chemical Co., Ltd. Sumibrite M140 Fluorine polymer: Asahi Glass Co., Ltd. Fluon CD-1 Phenyl silicone: Toray Dow Corning SH-
510

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[0078]

The thermoplastic resin composition of the present invention can be formed into a molded article having excellent low-temperature impact strength and good molded appearance, and is used for automobile parts, electric and electronic parts, and OA.
It can be used for various purposes such as equipment housing.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 51/00 C08L 51/00 53/00 53/00 101/00 101/00 F term (reference) 4J002 AC01Y AC07Y AC08Y AE04U BB03Z BB05Y BB06Y BB07Y BB07Z BB10Z BB12Z BB15Y BB15Z BB17Z BB18Y BC00Z BC07Z BC11U BG04Z BG05Z BG09Z BN12Y BN15Y BN16Y BN17Y BN21X BN22X BP01Y BP03Y CD12U CF00Y CF04Z CF05Z CF08Z CG01W CG02W CG03U CH07Z CK02Y CP03U DA056 DE076 DE126 DE146 DH056 DK006 EB086 EJ056 EU186 EW016 EW056 EW156 FD010 FD13U FD136

Claims (3)

[Claims] 1. A composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl monomers onto a composite rubber comprising a polycarbonate resin (A), a polyorganosiloxane component and a polyalkyl (meth) acrylate component. A thermoplastic resin composition comprising (B) and a rubbery polymer (C). 2. The thermoplastic resin composition according to claim 1, further comprising an olefin resin (D-1), a polyester resin (D-2), and a polyphenylene ether resin (D-3).
And a thermoplastic resin composition containing at least one selected from vinyl resins (D-4). 3. A thermoplastic resin composition further comprising a flame retardant (E) added to the thermoplastic resin composition according to claim 1.